Antharaquinone dyes and process of making them.



UNITED STATES PATENT OFFICE.

HEINRICH NER-ESHEIMER, 0F LUDWIGSBAFEN-GN-'lHE-BHINE, GERMANY, ASSIGNOH TO BA'JJISCHE ANILIN 8c SODA FEERIK, OF LUD N'IGS1 AFEN-ON-THE{RHINIEL GER- lVlANY, A CORPQRATION.

No Drawing.

To all 'nhom 1' I may; (ransom Be it known that I, llnmmcii Fiannsm-zmnzc. lh. 1)., chemist, subject of the Queen of the Netherlands, residing; at Lud' wigs-hal enwillie-Rhine, iei'nnimu, have invented new and useful improvements in inthruquinone lives and lrovesses of lVL-iliing Then'n of which the following is a specili :ution,

l have discovered that by suitably treating l--Ll1nl .'.l0 ii'Slllfi)-2.1.fli1llll\fifl(lllnOIlii :1'cri- (lones of a constitution corresponding to the general formula Nan co I (where R represents an a'ronm'tic residue), including derivatives of these compounds, the sulfonic acid group in position 3'65111 veiy easily ho split 0G. for instance, by menus oi limitacid. alkali, or reducing uncut. The proihnrtioi'i of 4 1miino-fl-sulfo- 2.1-21ntln'uquinon" HVJ'llIOIlES win he ctlectcrl lay treating 4 -;unino-1.-anvlnlo-unthmsuch conditions that. the smlt'onic :ui'iil group is immedintclv split oil from the position 3, and IHtGIXTXQtllziiI-B separation of the sulfonic and compound can he avonleil. In some cases the 'sulfonicacid group can be split oil in thedyeing bath, or even after the sulfonic acid has been applied tot-he fiber.

Specification of Letters Patent.

Application filefl Dctobcz 29, 1914.

ANTHRAQU INONE EYES AND PROCESS OF MAKING THEM.

Patented Dec. 1 2, 1.916.

Serial No. 869,167:

The amino-halogen-unthraquinonc acriilones of a constitution corresponding tolthe l'oi-lnulzi and \\'lll('ll are obtainable by splitting oil the sullonio acid group from the products produced from 'i--lC- )l parmhalogemorthocarbon anili lo unthrziquinone-3 -sulfonic uciil by the action of 23)? fuming llfurio avid at from to 25 C. have not hi'herfio been described in the literature. They consist when iii-y of dark bllJQPOWdGIS whicl are insoluble in vvntenlifiivultly soluble in organic solvents; of low boiling point, yieh'; blue soluiions in hot nitrohcnzene, figoni lnrown to yellow solutions in cement-rated sulfuric acid and with alkaline hydrosulfite gzive violet "Hi5 which (lye cotton greenish lue to blue shades.

The. following oxznnples will serve to illusu-guvt'ul'thei' the nature of this invention, which however, not confined to these exiunplen. The parts are by Weight:

l lxzunplc 1: Dissolvo ten parts of l amino- 1 ortho-nra1rhox3 nnilido anthraquinone-3- sulionio acid in one hundred parts ofchlorsultonic nciii, heat for half an hour atfrom to (30 (1., mldqsmne dilute sulfuric acid, pour onto ice, filter oii the-product and wash it well with :1 dilute solution of potassium tlllol'ltl. Then heat it with moder ately di lute sulfuric acid, whereupon the sulfonic acid group in position 3 of the unthraquinone. residue is split off and a pure wool dye is obtained which appezirs to be identical. with that obtainable by snlfonuting r.-:imino- 2.1 antlnuquinone acridone.

Example 2: Boil one part of i-amino-5- chlor 2l-anthrziquinone acriclone-3-sulf0nic acid (obtainable by touting 4 -zimino-1-parachlonortho-ciu'hoxyunilido anthmqninon cnot 3-sulfonic acid with 23% fuming sulfuric acid at from 20 to 25 C.) with fifty parts of trichlorbenzene, or nitrobenzene, until by a test portion, it is seen that no unaltered sulionic acid remains. Then allow the mass to coohand filter oil the 4-amino-5-chlor-2.1- anthraquinone acridone, and Wash it with airohol. It is a dark blue powder, which is insoluble in water and is very diflicultly soluble in organic solvents of low boiling point; it dissolves in boiling trichlor-benzone, anilin, and nitrobenzene, the solutions being blue and it yields a yellow-brown solution in concentrated sulfuric acid. It yields a violet vat with alkaline hydrosulfite and dyes cotton a clear and very fast greenish blue.

Example 3; Introduce ten parts of the potassium salt of l-amino-1 -anilido-anthraqumOne3-sulfo-2-carboxylic acid (obtainable by condensing l-amino-l-brom-anthraquinone-3-sulfo acid with potassium anthranilate) into one hundred parts of sulfuric acid monohydrate while at a temperature of from 120 to 125 C. .Maintain the yellow-brown solution for a short time at this temperature, then cool, pour into water, filter off the sulfonic acid and Wash with a dilute solution of potassium chlorid. During the reaction the acridone ring is formed, 'hc sulfonic acid group is split oil from position 3 and a sulfonic acid group enters the phenyl residue, since theproduct obtained appears to be identical with the sulfonation product of 4amino-2.1-anthraquinone acridone. It yields a pure blue solution in Water and in alcohol and a brown-yellow solution in comentratedsulfuric acid. It dyes wool, from an acid bath, fast blue shades.

Example 4: Introduce ten parts of the potassium salt of .4-amino'sLaniliddanthra quinone-3-sulfo-2'-carboxylic acid into a solution of seven parts of bromin in thirt' parts of sulfuric acid monohydrate and thirty-five parts of chlor-sulfonic acid, While maintaining temperature not above 15 G...

Then stir for a few hours at from 10, to 15 ,(1, heat for one hour at from 40, to 4:53 C. and then allow the product to flow slowly into two hundred parts of sixty-two per cent. sulfuric acid. Thenallow the mixture to stand at ordinary temperature until the elimination of the sulfonic acid group is complete (this requires usually 'from twenty, to thirty hours), and pour the mass into water and work up as usual. The prodis a broniinated 4-amino-2.1-antl1ra'- quinone acridone, probably substitutedin position 5 with bromin, and consists of a dark blue powder, which gives an orange solution in concentrated sulfuric acid. It dyes cotton from the vat pure blue shades.

Eqnnnplc 5: Digest together'attheordinary temperature t c parts of 4-amino-5" which consist when dry of dark blue powders containing halogen, are insoluble in water, difficultly soluble. in organic solvents of low boiling point, give blue solutions in' hot nitrobenzene, from brown to yellow solutions in concentrated sulfuric acid and which dissolve in alkaline hydrosulfite solution giving violet vats which dye cotton from greenish blue to pure blue.

' 2. The hereinbefore described anthraquin one dye being amino chlor-anthraquinone acridone, probably possessing a consti- 111G011 corresponding to the formula concentrated. sulfuric acid, and which dis solves in alkaline hydrosulfite solution giving, a violet vat, which dyes cotton greenish blue shadesof excellent fastness.

3. The'process of, producing 4-amino 2lanthraquinone acridones by treating a 4-an1ino-3-sulfo-2.l-anthraquinone 'acridone so as to split 011' the sulfonic acid group from position 3.

4. Thevproccss of producing -amino-Qi anthmquinoue ucridones by treating sl-zlmiuo 3-sulfo-2.l-anthraquinc.= awridones with an.

alkaline hydrosulfite sohition.

5. The process of producing amino-halogen-anthratulinone acridones of a constitu- 1 tion corresponding to the formula:

NH2 I l 2 \/\CO/\ 1//\C0 l HN 2 K/ HLl bytregiting the;corresponding sultonic acid compound con'utiuing the suliouicucid group in position 3 with alkaline hydrosulfite solution.

6. The process of producing amino-chlorunthI-uquinone ucridone of a constitution corresponding to the formula by treating: the sulfonic acid derivative thereof containing the sulfonic acid group in position 3 with an alkaline hydrosulfite solution.

In testimony whereof I have hereunto set my hand in the presence of two subscribing witnesses v HEINRICH: N'ERESHEIMER.

' -Witnesses:

H. MERLE CocuRAN, W. EuNsT. 

